GraspIT – OCR Module 5 Part 1

A. How Fast?
1. Chloromethane is hydrolysed in the atmosphere. The rate of this hydrolysis in the gas phase has
been investigated in the laboratory.
The equation for the hydrolysis reaction is given below.
CH3Cl + H2O  CH3OH + HCl
The rate was found by measuring the rate of formation of HCl. The results are given in the table
below:

Initial rate of formation

[CH3Cl ] /mol dm–3 [H2O] /mol dm–3 of HCl
Experiment
/mol dm–3 s–1
1 0.250 0.250 2.838
2 0.375 0.250 4.256
3 0.250 0.125 0.709

a. Use the data from the table to determine the orders of reaction with respect to
CH3Cl and H2O. [2]
CH3Cl = 1st order [1], H2O = 2nd order [1]
b. Give the rate equation and overall order for the reaction. [2]
Rate = k [CH3Cl] [H2O]2 [1] Overall order = 3 [1]
c. A chemist suggested that the mechanism for the reaction might be:
Step 1 2H2O ⇋ H3O+ + OH– fast
Step 2 CH3Cl + OH–  CH3OH + Cl – slow
Explain why this mechanism is consistent with the orders of the reaction in (a). [2]
2 molecules of H2O are required for the first step [1] of the reaction, until they react the
slow step involving CH3Cl cannot occur. [1]
d. A student found that another chloroalkane, (CH 3)3CCl, was readily hydrolysed by
water at 12 °C. He determined that the reaction was first-order with respect to
(CH3)3CCl and zero-order with respect to water.
At a (CH3)3CCl concentration of 1.82 × 10–3 mol dm–3, the rate of reaction was 1.56 × 10–4
mol dm–3 s–1.
Calculate the rate constant for the reaction and give its units. [3]
Rate = k [CH3Cl] [H2O]0 [1]
k = Rate/[CH3Cl] = 1.56 x 10-4/1.82 x 10-3 = .0857 [1] s-1 [1]

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 GraspIT – OCR Module 5 Part 1
2. Bromate ions BrO3– can react with bromide ions, Br ̄, in acidic solution to form bromine.
The equation for the reaction is:
BrO3–(aq) + 5Br–(aq) + 6H+(aq)  3Br2(aq) + 3H2O(l)

A student carried out a series of experiments using a colorimeter to find out the rate equation
for this reaction.

a. Explain why colorimetry can be used to follow this reaction. [2]

All reactants are colourless as is water [1] Bromine has colour / is red/brown so colour
appears as the reaction progresses [1]

b. The student’s processed results are given in the table below.

[BrO3¯(aq)] [Br –(aq)] [H+(aq)] relative

/ mol dm–3 / mol dm–3 initial rate
/ mol dm–3
0.01 0.02 0.001 1

0.01 0.02 0.004 4

0.02 0.02 0.004 8

0.01 0.04 0.004 16

Use the data in the table to work out the rate equation for the reaction. [3]
Rate = k [BrO3–] [ Br–]2 [H+] (1 for each correct power – 1,2,1)
c. Further experimentation found that at very low pH values the rate equation for the
reaction of BrO 3 –with Br – is different from that determined by the student. The rate
equation is given below.
Rate = k [BrO3– (aq)] x [Br –(aq)] x [H +(aq)]2

The experiment was carried out using the following concentrations:

[BrO3– (aq)] = 7.00 x 10–4 mol dm–3
[Br –(aq)] = 5.00 x 10–2 mol dm–3

[H+(aq)] = 2.00 x 10–1 mol dm–3

The rate of reaction was found to be 4.5 x 10–6 mol dm–3 s–1.
i) Calculate the numerical value of the rate constant for the reaction. Give your
answer to an appropriate number of significant figures. [2]
k = 4.5x10-6/7.00x10-4 x 5x10-2 x (2.00x10-1)2 [1] = 1.4x10-6 [1]
ii) Give the units of the rate constant. [1]
mol-3 dm9s-1

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 GraspIT – OCR Module 5 Part 1
d. It has been suggested that the slow, rate-determining, step of the reaction involved the
interaction of an intermediate, H2BrO3+, with Br –.
Rate = k [BrO3– (aq)] x [Br– (aq)] x [H+ (aq)]2

Explain how the orders of reaction support the chemists’ suggested rate-determining
step. [3]

2 H+ and a BrO3– are required to form the H2BrO3+ [1], until this forms no further
reaction can take place [1], Br– will then react with the intermediate, this is the RDS so
will appear in the rate equation. [1]

3. Peroxodisulfate ions will oxidise iodide ions to iodine in an aqueous solution. The half
equations are shown below.
S2O82– + 2e–  2SO42–
2I– + 2e–  I2
a. Write an ionic equation for the reaction between peroxodisulfate and iodide ions.
State symbols are not required. [1]
S2O82– + 2I– 2SO42– + I2 [1]
b. A student investigates the rate of this reaction at room temperature by using a
colorimeter. The student performs one experiment only in which a large excess of
peroxodisulfate ions to iodide ions is used. The student has a flask in which the reagents
are mixed.
Describe how the student could use a colorimeter to measure the concentrations
of iodine in the flask as the reaction proceeds.
In your answer:
 Describe the procedures the student would carry out. Assume that samples of
required solutions are available.
 State the measurements that would be recorded and indicate how these can
be converted into concentrations of iodine. [6]
1. use filter of complementary colour to iodine/solution [1]
2. zero colorimeter with water [1]
3. measure absorbance readings of standard solutions/solutions of known
concentration (of iodine) [1]
4. plot calibration graph [1]
5. take absorbance readings of the reacting mixture at known/certain times AW (must
refer to time – may state units of time) [1]
6. convert absorbance readings to iodine concentrations using the calibration curve [1]

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 GraspIT – OCR Module 5 Part 1
c. The student’s results for the reaction are given below.

Experiment [S2O 8 2–] [I–] Rate of formation of

–3 / mol dm–3
/ mol dm iodine, I2
/ mol dm–3 s–1
1 0.075 0.040 2.0 × 10–5
2 0.150 0.040 4.0 × 10–5
3 0.075 0.020 1.0 × 10–5
i. Complete the rate equation for the reaction. Rate = k × ………… [1]
Rate = k ×[S2O82–] [I–]
ii. Calculate the rate constant, k, for the reaction and give its units. [3]
k = Rate/ [S2O82–] [I–] [1] = 2.0 × 10–5/(0.075 x 0.04) = 75 [1]
Units of k = mol-1 dm3 s-1 [1]
iii. What would be the rate of disappearance of I – in experiment 3? [2]
2 x rate of appearance of I2 [1] 2x10-5 [1]

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 GraspIT – OCR Module 5 Part 1
B. How far?
1. Write the equilibrium expression, Kp, for each of the following reactions. [3]
a. 2 NO(g) + O2(g) ⇌2 NO2(g) Kp = [NO2]2/[NO]2 [O2]
b. 4 HCl(g) + O2(g) ⇌2 H2O(g) + 2 Cl2(g) Kp = [H2O]2[O2] /[H2O ]2 [Cl2]2
c. NOCl(g) ⇌NO(g) + ½ Cl2(g) Kp = [NO]/[NO] /[Cl2 ]1/2
2. The following equilibrium pressures at 800K were observed for the reaction shown below.
Calculate Kp for this reaction. [2]
2N02(g) ⇋ 2NO(g) + 02(g)
pNO2 = 5.50kPa pNO = 6.5x10-3kPa p02 =4.5x10-3 kPa

Kp = [NO]2[O2] /[N2 O]2 [1] = (6.5x10-3)2 x 4.5x10-3 /(550)2 = 6.28x10-9 [1] kPa

3. Phosphorous trichloride gas and chlorine gas react to form phosphorous pentachloride gas:
PCl3(g)+Cl2(g)  PCl5(g)
A gas vessel is charged with a mixture of PCl 3 (g) and Cl2 (g), which is allowed to equilibrate at 450
K. At equilibrium the partial pressures of the three gases are: PCl 3 = 124 kPa, Cl2 = 157 kPa, and
PCl5 = 130 kPa.
a. What is the value of Kp at this temperature? [2]
Kp = [PCl5] /[PCl3 ] [Cl2] [1] = 130/(124x157) = .0067 kPa -1 [1]

b. Does the equilibrium favour reactants or products?

Reactants as Kp value is small / less than 1

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 GraspIT – OCR Module 5 Part 1
4. At 1000 K, the equilibrium partial pressures for the reaction below are:
CH4 =20 kPa, H2S = 25 kPa, CS2 = 52 kPa, and H2 =10 kPa.
What is the value of Kp? [2]
CH4(g) +2H2S(g)  CS2(g) +4H2(g)
Kp = [CS2] [H2] / [CH4] [H2S] [1] = (52 x(10)4 )/ (20 x (25)2) = 41.6 kPa2 [1]
4 2

5. Hydrogen gas reacts with iodine gas to form hydrogen iodide:

H2(g) + I2(g) ⇌ 2HI

1.6 mol H2 is mixed with 1.4 mol I2 at constant temperature. At equilibrium, the mixture contains
0.40 mol H2 and the total pressure is 1.8 MPa.
a. Calculate the number of moles of each gas at equilibrium. [1]
H2 = 0.4 I2= 0.2 HI = 2.4 [1]

b. Calculate the mole fraction of each gas at equilibrium. [2]

H2 = 0.4 /3= 0.133 I2= 0.2 /3 = 0.667 HI = 2.4/3 = 0.800 [2]

c. Calculate the partial pressure of each gas at equilibrium. [2]

H2 = 0.133 x 1.8x106 = 2.394x105 I2= 0.667 x 1.8x106 = 1.2.6x106
6 6
HI = 0.800 x 1.8x10 = 1.44x10 [2]

d. Calculate Kp at this temperature, including units. [3]

Kp = [1.44x106]2 / (2.394x105 x 1.26x106) [1] = 6.874 [1] No units of Kp [1]

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 GraspIT – OCR Module 5 Part 1
C. Acids, bases and pH.
1. This question is about Brønsted–Lowry acids and bases.
a. Define the term Brønsted–Lowry acid. [2]
A proton donor

b. For each reaction, indicate whether the underlined substance is acting as a Brønsted–
Lowry acid (A) or a Brønsted–Lowry base (B) by writing A or B under each chemical. [3]
i. HNO3 + H2SO4 ⇋ H2NO3+ + HSO4–- B
ii. CH3NH2 + H20 ⇋ CH3NH3+ + OH– A
– +
iii. CH3COOH + H2O ⇋ CH3COO + H30 B

2. This question is about the pH of some solutions containing a strong alkali and a weak acid
Give all values of pH to 2 decimal places.
a. Write an expression for pH. [1]
pH = -Log[H+]

b. Write an expression for the ionic product of water, Kw. [1]

Kw = [H+][OH–]

c. What is the pH of a 0.0025 mol dm-3 solution of the strong alkali KOH? [2]
[H+] = Kw/[OH–] = 1x10-14/0.0025 = 4x10-12 (1) pH = -Log[4x10-12] = 11.4 (1)

d. At 25 °C, the acid dissociation constant Ka for ethanoic acid has the value
1.75 x 10–5 mol dm–3.
i. Write an expression for Ka for ethanoic acid. [1]
Ka = [CH3COO–][H+] / [CH3COOH]

ii. Calculate the pH of a 0.125 mol dm–3 solution of ethanoic acid at 25 °C. [2]
[H+] = √ka[CH3COOH] = 1.479x10-3 (1) pH = –log[1.479x10–3] = 2.83 (1)

e. Calculate the pH of the solution formed when 10 cm 3 of 0.120 mol dm–3 potassium
hydroxide are added to 20.0 cm3 of 0.120 mol dm–3 ethanoic acid at 25 °C. (Ka for
ethanoic acid = 1.75 x 10–5 mol dm–3. [4]
KOH + CH3COOH  CH3COO–K+ + H2O
0.0012 mol + 0.0024 mol (1)
0.0012 mol ethanoic acid and 0.0012 mol ethanoate ions (1)
[H+] = ka[CH3COOH]/[CH3COO–] = 1.75x10-5 (1)
pH = –log[1.75x10–5] = 4.76 (1)

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 GraspIT – OCR Module 5 Part 1
3. The titration curves below, labelled A, B, C and D, are for combinations of different solutions of
acids and bases.
All solutions have a concentration of 0.2 mol dm –3.

A B

C D

a. From the curves A, B, C and D, choose the curve produced by the addition of
i. nitric acid to 25 cm3 of potassium hydroxide C
ii. ammonia to 25 cm3 of hydrochloric acid D
iii. sodium hydroxide to 25 cm3 of ethanoic acid B [3]

b. The table below shows a selection of indicators with the pH range they change colour
over and the colours in acid and alkaline solution.

Indicator Colour in acid pH range Colour in alkali

Crystal violet yellow 0.2-1.7 blue
Congo red blue-violet 3.0-5.0 red
Cresol Red yellow 7.2-8.8 reddish-purple
Alizarin Yellow R yellow 10.2-12.0 red

i. Which indicator would be most suitable for detecting the end point in titration A
but not in titration B? [1]
Congo red

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 GraspIT – OCR Module 5 Part 1
ii. In titration C cresol red was used as an indicator. What colour change would you
expect to see at the end point of this titration? [1]
Reddish purple to yellow

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 GraspIT – OCR Module 5 Part 1
4. Describe how a mixture of ethanoic acid and its salt, sodium ethanoate, can act as a buffer
solution when small quantities of alkali are added to the mixture. In your answer you should
refer to the equilibrium below:
CH3COOH ⇋ CH3COO– + H+ [4]

The mixture of the acid and it salt contains large quantities (1) of both undissociated ethanoic
acid and ethandioate ions. (1) Addition of a small amount of OH – will cause more ethanoic acid
to dissociate to react with the OH– (1) and equilibrium / pH is restored (1)

5. A buffer solution was made containing propanoic acid (Ka = 1.34 x 10 -5 mol dm-3) at a
concentration of 0.1 mol dm-3 and sodium propanoate at a concentration of 0.5 mol dm -3.
Calculate the pH of the solution. [2]
[H+] = Ka[propanoic acid]/[propanoate ions] = 3.4x10 -5 x 0.1/0.5 = 6.8x10-5 (1)
pH = –log[6.8x10-5] = 5.17 (1)

6. A student prepared a buffer solution as follows:

To 1.00 dm3 of 0.200 mol dm-3 ethanoic acid, 16.40g of solid sodium ethanoate (RFM = 82) was
added. The solution was agitated until the sodium ethanoate had all dissolved.
Ethanoic acid has a Ka of 1.8x10-5.

a. What will be the pH of the original ethanoic acid solution? [2]

[H+]= √Ka[ethanoic acid] = √1.8x10-5 x 0.200 = 3.6x10-6 (1)
pH = -log(3.6x10-6) = 5.44 (1)

b. What will be the pH of the solution after the addition of sodium ethanoate? [2]
[H+]= Ka[ethanoic acid]/[sodium ethanoate] (1) = 1.8x10-5 x 0.200/0.2 (1) = 1.8x10–5
pH = -log(1.8x10–5 = 4.745 (1.74 or 1.75) (1)

c. 0.010 moles of hydrochloric acid are added to the buffer solution, calculate the pH of the
resulting solution. [3]
Ethanoic acid concentration falls to 0.19 mol dm -3 and ethanoate ion concentration rises
to 0.21 mol dm–3 (1)
[H+]= Ka[ethanoic acid]/[sodium ethanoate] (1) = 1.8x10-5 x 0.190/0.210 = 1.63x10–5 (1)
pH = -log(1.63x10–5) = 4.79 (1)

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